JP2005075847A - Polyproylene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent heat distortion and extraction resistances and to provide a material having even good transparency. <P>SOLUTION: The polypropylene resin composition comprises at least one kind of nucleating agent selected from a sorbitol nucleating agent and a phosphate nucleating agent in an amount of 0.01-0.50 pt. wt. based on 100 pts. wt. of a polypropylene resin having ≥0.960 isotactic pentad fraction and ≤4.5 molecular weight distribution (Mw/Mn) and at least one kind of amine compound selected from a dialkylhydroxylamine, a hydroxyalkyl group-containing amine and a hindered amine in an amount of 0.01-0.20 pt. wt. based on 100 pts. wt. of the polypropylene resin. The resin composition has excellent rigidity and heat distortion and extraction resistances and even good transparency and can particularly suitably be used as a member of food containers and medical containers. The balance of the rigidity and the transparency can suitably be selected according to the purpose of uses of molded products by selecting the polypropylene resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polypropylene resin composition. Specifically, it is a resin composition excellent in rigidity and heat distortion resistance, and excellent in extraction resistance, and also has good transparency, so that it can be suitably used particularly as a member for food containers and medical containers. Articles and molded articles thereof are provided.

  Polypropylene resins are typically manufactured with Ziegler-Natta catalysts (ZN catalysts), and have excellent heat resistance, chemical resistance and rigidity, and are widely used as materials for injection molding, film molding, sheet molding, blow molding, etc. Has been. Moreover, in order to improve the transparency, it is common practice to copolymerize a small amount of ethylene or the like with propylene.

  However, the ZN-catalyzed polypropylene-based resin has a limit in transparency as a polymer, and as an improvement, various additives for improving the transparency include metal salts of carboxylic acids (Patent Document 1) and sorbitol. A resin composition containing a nucleating agent (Patent Document 2), an aromatic phosphate (Patent Documents 3 and 4) and the like has been proposed. As a result of these efforts, polypropylene resins are being expanded into various transparent materials, but when applied to food containers and medical containers, the presence of odors and trace amounts of elution components may become a problem. Further improvements are desired. Proposals for combining various antioxidants with carboxylates (Patent Documents 5 and 6) have also been made.

  On the other hand, an attempt to use a propylene polymer obtained by a metallocene catalyst as a polypropylene resin having a low soluble content has been proposed (Patent Document 7). Although this resin is characterized by low soluble components, it is still insufficient in terms of state stability at high temperatures.

Among them, since the extraction amount is small, in a resin composition that can be suitably used as a food container, a medical container, or a medical device, a polypropylene-based weight that can maintain state stability at high temperatures and exhibits good transparency. There is a great demand for a resin composition comprising a coalescence. However, a resin composition that achieves state stability at high temperatures cannot provide sufficient transparency, and conversely, a resin composition that excels in transparency exhibits state stability at high temperatures and resistance to contents. There were problems such as poor elution.
JP-A-9-59458 JP-A-4-339847 JP-A-1-178541 JP-A-2-49047 JP-A-11-172058 JP-A-11-302469 Japanese Patent Laid-Open No. 9-296084

  As described above, the propylene resin composition obtained by blending various additives with the propylene polymer obtained with the ZN catalyst has a certain level of transparency and mechanical properties, In order to apply to applications requiring sanitary properties such as food containers and medical containers, it is required to develop materials that maintain state stability at high temperatures, have little elution, and have excellent transparency.

  As a result of intensive studies in view of the above problems, the present inventors have dramatically improved transparency by using a plurality of specific additives in a polypropylene polymer having certain specific physical properties. At the same time, the present inventors have found a resin composition that has few components to elute and has good rigidity characteristics, and has reached the present invention.

  That is, according to the first aspect of the present invention, the isotactic pentad fraction is 0.960 or more and the molecular weight distribution (Mw / Mn) is 4.5 or less, based on 100 parts by weight of a polypropylene resin. 0.01 to 0.50 parts by weight of at least one nucleating agent selected from sorbitol nucleating agents and phosphate nucleating agents, and at least one amine selecting from dialkylhydroxylamine, hydroxyalkyl group-containing amine and hindered amine It is a polypropylene resin composition containing 0.01 to 0.20 parts by weight of a compound.

  The second invention of the present invention is based on 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. It is a polypropylene resin composition containing 0.01 to 0.50 parts by weight of a sorbitol-based nucleating agent and 0.01 to 0.20 parts by weight of a dialkylhydroxylamine or a hydroxyalkyl group-containing amine.

  The third invention of the present invention is based on 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. It is a polypropylene resin composition containing 0.01 to 0.50 parts by weight of a sorbitol nucleating agent and 0.01 to 0.20 parts by weight of a hindered amine.

  The fourth invention of the present invention is based on 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. It is a polypropylene resin composition containing 0.01 to 0.30 parts by weight of a phosphate nucleating agent and 0.01 to 0.10 parts by weight of a dialkylhydroxylamine or hydroxyalkyl group-containing amine.

  The fifth aspect of the present invention relates to 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. A polypropylene resin composition containing 0.01 to 0.30 parts by weight of a phosphate nucleating agent and 0.01 to 0.10 parts by weight of a hindered amine.

  The sixth invention of the present invention is the polypropylene resin composition, wherein the polypropylene resin composition further contains 0.01 to 0.10 parts by weight of a dicarboxylic acid metal salt of a crosslinked cyclic hydrocarbon compound. It is.

  Moreover, 7th invention of this invention is a polypropylene resin composition in which the said polypropylene resin composition contains 0.01 to 0.30 weight part of hydrotalcites further.

  The eighth invention of the present invention is a polypropylene resin composition wherein the polypropylene resin composition further contains 0.01 to 0.20 parts by weight of a higher aliphatic carboxylic acid metal salt.

  The ninth invention of the present invention is a polypropylene resin wherein the total amount of hydrotalcite and higher aliphatic carboxylic acid metal salt is 0.02 to 0.30 parts by weight in the polypropylene resin composition. It is a composition.

  The tenth invention of the present invention is a polypropylene resin composition in which the polypropylene resin is obtained using a metallocene catalyst.

  The eleventh aspect of the present invention is a food container or a medical container formed by molding the polypropylene resin composition.

  The twelfth aspect of the present invention is a substantially non-stretched film, uniaxially stretched film, biaxially stretched film, injection molded body, extruded molded body, blow molded article formed by molding the polypropylene resin composition. It is a molded body or a sheet.

  The polypropylene resin composition of the present invention is a resin composition excellent in rigidity and heat distortion resistance and excellent in extraction resistance, and also has good transparency, and is particularly suitable as a member for food containers and medical containers. Can be used. By selecting a polypropylene resin raw material, the balance between rigidity and transparency can be appropriately selected according to the intended use of the molded product.

  For example, when a copolymer of propylene and an α-olefin other than propylene (propylene / ethylene random copolymer) is selected as the polypropylene resin, the polypropylene resin composition is 2 mm thick by injection molding In addition, it is possible to obtain a highly transparent molded article having a haze of less than 35% and a flexural modulus of 900 to 1200 MPa. Further, when a propylene homopolymer is selected as the polypropylene resin, the polypropylene resin composition is injection-molded to achieve a rigidity of 35 to 50% haze and a flexural modulus of 1500 to 2500 MPa when the thickness is 2 mm. An excellent molded body can be obtained.

Embodiments of the invention will be specifically described below.
1. Polypropylene resin The polypropylene resin of the present invention has an isotactic pentad fraction [mmmm] of 0.960 or more and a molecular weight distribution (Mw / Mn = Q value) of 4.5 or less. [Mmmm] is measured by ¹³ C-NMR, and the Q value is measured by gel permeation chromatography (GPC), which will be described in detail later.

  The polypropylene resin is a homopolymer of propylene or a copolymer of propylene and another α-olefin other than propylene. As the α-olefin (comonomer) other than propylene, ethylene or an α-olefin having 4 to 12 carbon atoms is used. In the case of the copolymer, the content of ethylene or the α-olefin having 4 to 12 carbon atoms is more than 0 and 20% by weight or less. Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and preferably ethylene, 1-butene, 1-hexene.

The comonomer content in the copolymer is 20% by weight or less, preferably 0.5 to 10% by weight, and more preferably 1 to 8% by weight. If the comonomer exceeds 20% by weight, the rigidity as a molded container is insufficient and the amount of soluble components increases, which is not preferable. On the other hand, if the amount is too small, the effect of adding the comonomer is not exhibited. The comonomer content can be calculated from the measurement result of ¹³ C-NMR.

Next, a method for measuring the isotactic pentad ratio ([mmmm]) will be described. About 100 mg of a polypropylene polymer sample was dissolved in a mixed solvent of 2 ml of orthodichlorobenzene (ODCB) and 0.2 ml of benzene, and a resonance frequency of 125 MHz was obtained using a 500 MHz NMR apparatus (manufactured by Varian, Inova 500). the ¹³ C-NMR measured in .7MHz, the obtained spectrum, "Macromolecules Vol. 20 (1987), 616-620 pages" and "Macromolecules Vol. 21 (1988), pp. 617-622" described Based on the above method, each peak is assigned and the ratio of [mmmm] in all pentads is obtained. In addition, it is the value calculated excluding the methyl carbon peak corresponding to a heterogeneous bond or a comonomer.

  The value of [mmmm] is 0.960 or more, preferably 0.975 or more, more preferably 0.990 or more. When [mmmm] is less than 0.960, the stability in a high temperature state is lowered, so that soluble components and components causing odor increase, which is not preferable. In particular, when the polypropylene resin is a propylene copolymer, the stability at high temperatures tends to decrease.

Another feature of the polypropylene resin of the present invention is that the molecular weight distribution (Mw / Mn) measured by the GPC method is 4.5 or less. The weight average molecular weight (Mw), number average molecular weight (Mn), and Mw / Mn are measured by the following methods. Further, the conversion from the retention volume to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene.
Standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL.
The calibration curve uses a cubic equation obtained by approximation by the least square method.

  In the viscosity formula [η] = K × Mα used for conversion to molecular weight, the following numerical values are used as K and α.

PS: K = 1.38 × 10 ⁻⁴ , α = 0.78
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78
The measurement conditions for GPC are as follows.
Apparatus: GPC manufactured by Waters (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: ο-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection amount: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve at 140 ° C. for about 1 hour.

  The weight average molecular weight (Mw) of the obtained polypropylene polymer is usually in the range of 50,000 to 2,000,000, preferably 150,000 to 1,000,000 in terms of polypropylene. On the other hand, Mw / Mn is 4.5 or less, preferably 4.0 or less, and more preferably 3.0 or less. If it is 4.5 or more, low molecular weight compounds having a molecular weight of 5000 or less are increased, and they are thermally decomposed under a high temperature condition to be transformed into soluble or volatile components, which is not preferable.

<Method for producing polypropylene polymer>
If the polypropylene polymer used by this invention has the physical-property value ([mmmm] and Q value) described previously, the manufacturing method will not be specifically limited. Although it can be produced using a specific Ziegler-Natta catalyst (ZN catalyst) known as a highly stereoregular catalyst, it can be preferably produced using a metallocene catalyst.

  Examples of such highly stereoregular catalysts include solid components (component A) and organoaluminum compounds (component B) that require titanium, magnesium, halogen, and specific electron donating compounds, and electron donating compounds as optional components. A so-called metallocene comprising a so-called ZN catalyst such as a catalyst comprising (C component), a metallocene complex (A ′ component), and an organoaluminum oxy compound, Lewis acid, anionic compound, or clay mineral promoter component (B ′ component) A catalyst is used.

The organoaluminum compound (component B) in the ZN catalyst has a general formula R ¹ _m AlX _3-m (wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen, and m represents 1 to 3). Can be used. Examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, alkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and ethylaluminum sesquichloride, and alkylaluminum hydrides such as diethylaluminum hydride. Also, alumoxanes such as methylalumoxane and butylalumoxane can be used.

In addition, as a titanium compound serving as a supply source of titanium constituting a solid component (component A) which essentially contains titanium, magnesium, halogen and a specific electron donating compound, a general formula Ti (OR ² ) _4-n X _n (Wherein R ² is a hydrocarbon residue having 1 to 10 carbon atoms, X is a halogen, and n is a number from 0 to 4). Among them, titanium tetrachloride, tetra Ethoxy titanium, tetrabutoxy titanium and the like are preferable.

  Examples of the magnesium compound that serves as the supply source of magnesium include dialkyl magnesium, magnesium dihalide, dialkoxy magnesium, and alkoxy magnesium halide, among which magnesium dihalide is preferable. Examples of the halogen include fluorine, chlorine, bromine, and iodine. Among them, chlorine is preferable, and these are usually supplied from the titanium compound or the magnesium compound, but aluminum halide, silicon halide, It may be supplied from other halogen sources such as tungsten halide.

Examples of electron donating compounds include alcohols, phenols, ketones, ethers, aldehydes, carboxylic acids, oxygen-containing compounds such as organic acids or inorganic acids and their derivatives, ammonia, amines, nitriles, isocyanates, etc. And the like. Among them, ethers, inorganic acid esters, organic acid esters, organic acid halides, organic silicon compounds and the like are preferable, silicic acid esters, substituted succinic acid esters, More preferred are polyvalent carboxylic acid esters such as phthalic acid esters, acetic acid cellosolve esters, phthalic acid halides, diethers, and organic alkoxysilicon compounds. For example, the general formula R ³ R ⁴ _3-p Si (OR ⁵⁾ such as t-butyl-methyl-dimethoxysilane, t-butyl-methyl-diethoxysilane, cyclohexyl-methyl-dimethoxysilane, cyclohexyl-methyl-diethoxysilane, etc. _P (wherein R ³ represents a branched aliphatic hydrocarbon residue having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon residue having 5 to 20 carbon atoms, preferably 6 to 10 carbon atoms). R ⁴ represents a branched or straight-chain aliphatic hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and R ⁵ is an aliphatic group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Represents a hydrocarbon residue, and p is a number from 1 to 3.), for example, 2,2-diisopropyl-1,3-diether, 2,2-diisobutyl-1,3- Has a 2,2-substituent such as diether Preferable are carboxylic acid esters such as 1,3-diethers, butyl phthalate, octyl phthalate, dibutyl 1,2-diisopropyl succinate, and phthalic acid halides such as phthalic chloride. It is also possible to use a plurality of these in combination. Particularly preferred are 1,3-diethers, coexistence of 1,3-diethers, combined use of 1,3-diethers and organosilicon compounds represented by the above general formula, or phthalic acid esters and phthalic acid chlorides. The combined use of a phthalic acid derivative such as the above and an organosilicon compound represented by the above general formula is particularly preferable. These preferable electron donors can be used as an electron donating compound (component C) not only during the production of the solid catalyst component but also during the polymerization in contact with the organoaluminum.

  As for these ZN catalysts, for example, JP-A-57-63310, JP-A-60-23404, JP-A-62-187706, JP-A-62-212407, JP-A-63-235307, JP-A-2-160806, JP-A-2-163104, JP-A-3-234707, JP-A-3-706, JP-A-3-294304, JP-A-7-258328, JP-A-8-20607, It is described in each gazette such as Kaihei 8-151407.

  Next, the metallocene catalyst will be described. As the metallocene compound (component A ′) in the metallocene catalyst, there are carbon bridges, silicon, germane bridge groups, and group 4 group having substituted or unsubstituted cyclopentadiene, indene, fluorene, and azulene as ligands. It is a transition metal compound.

  Non-limiting specific examples include: (1) Carbon bridges include ethylene bis (2,4-dimethylindenyl) zirconium chloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, isopropylidene ( 3-methylindenyl) (fluorenyl) zirconium chloride, isopropylidene (2-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, and the like.

  (2) Examples of the silicon bridge include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-isopropyl-4). -(3,5-diisopropylphenyl) indenyl) zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, silafluorenylbis (2-ethyl-4- (4-t-butyl) Phenyl) indenyl) zirconium dichloride, dimethylsilylene bis (2-ethyl-4- (4-chlorophenyl) azurenyl) zirconium dichloride, dimethylsilylene bis (2-ethyl-4- (4-t-butyl-3-chlorophenyl) az ) Zirconium dichloride, dimethylsilylene bis (2-ethyl-4- (3-fluoro-biphenylylmethyl) azulenyl) zirconium dichloride and the like.

  (3) As the germane crosslinking, a compound in which the silicon-crosslinked silylene of the above (2) is replaced with germanylene is used. A compound in which zirconium is replaced with hafnium is exemplified as a suitable compound as it is. Furthermore, the dichloride of the exemplified compound can be exemplified by other halides, compounds substituted with methyl group, isobutyl group, phenyl group, hydride group, dimethylamide, diethylamide group, etc. as suitable compounds.

  As a co-catalyst (B ′ component) used for the metallocene catalyst, an organoaluminum oxy compound, a Lewis acid, an ionic compound, and a clay mineral can be used.

  (1) Examples of organoaluminum oxy compounds include methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, butylboronic acid aluminum tetraisobutylmethylaluminum bispentafluorophenoxide, and the like.

(2) As the Lewis acid, a compound represented by BR ₃ (wherein R is a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group). For example, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane , Tris (p-tolyl) borane, tris (o-tolyl) borane, tris (3,5-dimethylphenyl) borane and the like, and inorganic compounds such as magnesium chloride and aluminum oxide are also exemplified.

  (3) Examples of the ionic compound include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt. Specifically, as the trialkyl-substituted ammonium salt, for example, triethylammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) aluminate and the like can be mentioned. Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetra (phenyl) borate. Examples of ionic compounds other than ammonium salts include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, ferrocenium tetra (pentafluorophenyl) borate and the like.

  (4) Examples of clay minerals include montmorillonite, mica, teniolite, hectorite, modified products treated with these acids and bases, and complexes with other inorganic oxides.

  Of these, in the promoter system using clay mineral, the effect of the composition of the present invention is particularly remarkable.

  In the propylene polymerization of the present invention, the amount of component (A), component (B) and component (C) used may be arbitrary as long as the effect of the present invention is observed, but generally falls within the following range. Is preferred. Component (A) is 0.01-1000 mol. ppm, and the amount of component (B) used is 0.1 to 10000 mol. ppm, preferably 1-1000 mol. ppm, more preferably 10 to 300 mol. Within the ppm range. Moreover, the usage-amount of a component (C) is 0-100 mol. With respect to the propylene supplied to a reactor. ppm, preferably 0 to 50 mol. ppm, particularly preferably 0 to 20 mol. It is within the range of pm.

  On the other hand, the component (A ′) and the component (B ′) in the case of the metallocene catalyst have a component (A ′) of 0.001 to 100 mol. The amount of ppm and component (B ') used is generally 10 to 100,000 (mol / mol) relative to component (A').

<Polymerization process>
As a polymerization method for producing the propylene polymer of the present invention, any polymerization method can be used as long as the target polypropylene polymer of the present invention is obtained. Examples thereof include slurry polymerization using a hydrocarbon solvent, bulk polymerization using propylene as a solvent, solution polymerization, and gas phase polymerization. Among these, slurry polymerization, bulk polymerization, and gas phase polymerization are preferable, and bulk polymerization and gas phase polymerization are more preferable.

  Polymerization is performed, for example, by supplying the above catalyst to a polymerization tank. The polymerization can take any form such as continuous polymerization, batch polymerization, and semi-batch polymerization. Among these, batch polymerization and continuous polymerization are preferable, and continuous polymerization is most preferable in terms of high productivity.

  As the polymerization tank, any conventionally known polymerization tank can be used. That is, a tank type stirred polymerization tank, a loop type polymerization tank, a fluidized bed type polymerization tank, a stirred fluidized bed type polymerization tank, and the like can be used. As long as the target propylene polymer can be produced, the polymerization tank may be used alone, or a plurality of polymerization tanks may be connected in series and / or in parallel.

  As the olefin supplied to the polymerization tank, propylene is mainly used, and in the case of copolymerization, ethylene, 1-butene, 1-pentene, hexene, octene or the like is used as a comonomer. In addition, inactive hydrocarbon compounds, such as methane, ethane, and propane, may be contained in propylene and a comonomer.

  Further, hydrogen may be used supplementarily in order to control the molecular weight of the olefin polymer. There is no restriction | limiting in particular in the supply amount of hydrogen, What is necessary is just to supply the quantity of hydrogen required in order to obtain desired molecular weight according to the property of the catalyst to be used. It is preferable to control the hydrogen supply amount by using the measured value of the hydrogen supply rate by the flow meter and the measured value of the hydrogen concentration in the polymerization tank by the process gas chromatograph in combination.

In the present invention, the polymerization temperature, polymerization pressure, average residence time and the like are not particularly limited. These can be arbitrarily set depending on the capability of the process, the performance of the catalyst, economic reasons, and the like. Generally, the polymerization temperature is about 20 to 200 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is atmospheric pressure to about 300 kg / cm ² G, preferably atmospheric pressure to about 100 kg / cm ² G. The average residence time is about 0.1 to 10 hours, preferably about 0.2 to 6 hours.

2. Nucleating Agent As the nucleating agent of the present invention, at least one selected from sorbitol nucleating agents and phosphate nucleating agents is used. Usually, the sorbitol-based nucleating agent and the phosphate-based nucleating agent are each used alone, but can also be used in combination as a mixture. The nucleating agent is also referred to as a nucleating agent, but is simply described as a nucleating agent in the present specification.

2.1 Sorbitol Nucleating Agent As the sorbitol nucleating agent, dibenzylidene sorbitol represented by the general formula (1) or a derivative thereof is used.

(Wherein X ¹ and X ² represent a hydrogen atom or a saturated aliphatic alkyl group having 1 to 4 carbon atoms, a branched alkyl group, an alkoxy group or a halogen atom, and X ¹ and X ² are the same or different. M and n represent an integer of 1 to 5, and m and n may be the same or different. P represents 0 or 1.)
Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, , 3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) ) Sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4 Di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol, , 3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) Sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methyl Benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzyl 2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, etc. can do. In particular, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, etc. Is exemplified.

  The amount of the sorbitol nucleating agent used is 0.01 to 0.50 parts by weight, preferably 0.05 to 0.30 parts by weight with respect to 100 parts by weight of the polypropylene resin. If the amount is less than 0.01 parts by weight, the effect of improving the transparency and rigidity by the nucleating agent cannot be obtained, and if the amount exceeds 0.5% by weight, the increase in the improving effect as a nucleating agent does not increase. Is unfavorable because it tends to increase or the amount of eluate tends to increase when used as a container.

2.2 Phosphate-based nucleating agent Examples of the phosphate-based nucleating agent used in the present invention include a phosphate ester-based metal salt nucleating agent, and in particular, represented by general formula (2) or general formula (3). One or a mixture of two or more selected from the aromatic phosphate metal salts to be used is preferably used.

(Here, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are the same. Or M may be a 1-3 valent metal atom, and n is an integer of 1-3.)

(Here, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are the same. Or M may be 1 to 3 metal atoms, and m is 1 or 2.

  Specific examples of the compound represented by the general formula (2) include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene- Bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2′-ethylidene -Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2 ' -Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, Thorium-2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium 2,2′-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate Fate, calcium-bis- (2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2′-methylene-bis (4,6-di-) t-butylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2 -Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2 ' -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t- Butylphenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4 6-di-t-butylfell) phosphate] and aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], among which sodium- 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

In the general formula (3), it is particularly preferable that R ² and R ³ are both t-butyl groups, particularly bis (2,4,8,10-tetra-t-butyl-6-oxo-12H-dibenzo [1 , 3,2] dioxaphosphocin-6-oxide) aluminum hydroxide salt is preferred. As a compounding quantity, it is 0.01-0.5 weight part with respect to 100 weight part of polypropylene-type resin, Preferably it is 0.03-0.3 weight part, Most preferably, it is 0.05-0.2 weight part. is there. If the blending amount is less than this range, the intended transparency improving effect is not obtained. Conversely, if it exceeds this range, the transparency improving effect according to the blending amount is saturated and it is not economical.

3. Amine-based compound In the present invention, at least one amine compound selected from dialkylhydroxylamine, hydroxyalkyl group-containing amine and hindered amine is used. Usually, a dialkylhydroxylamine, a hydroxyalkyl group-containing amine and a hindered amine are each used alone, but may be used in combination as a mixture.

  It is presumed that the amine compound improves the dispersibility of the nucleating agent exhibiting weak acidity by keeping the polypropylene resin composition weakly basic. When a hindered amine is used as the amine compound, the light stabilizing effect of the compound can be enjoyed together.

3.1 Dialkylhydroxylamine Dialkylhydroxylamine is represented by the general formula R ₂ NOH (wherein R represents the same or different alkyl group having 5 to 30 carbon atoms, preferably 8 to 20 carbon atoms). Specific examples include dioctylhydroxylamine, didecylhydroxylamine, didodecylhydroxylamine, dioctadecylhydroxylamine, diicosylhydroxylamine and the like. Mixtures of dialkylhydroxylamines with different alkyl groups can also be used.

3.2 Hydroxyalkyl Group-Containing Amine Hydroxyalkyl group-containing amines include nitrogen atoms of higher aliphatic amines such as decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, and two hydrogens bonded thereto. Examples include various compounds in which one or more ethylene oxides are added between atoms, and aliphatic diethanolamine, which is a compound in which one ethylene oxide is added between a nitrogen atom and two hydrogen atoms. Examples thereof include polyoxyethylene alkylamines in which a plurality of ethylene oxides are added. In addition, among the above fatty acid esters of various ethylene oxide adducts, only one of the two alcoholic hydroxyl groups of the ethylene oxide adduct is esterified with an aliphatic carboxylic acid having 8 to 30 carbon atoms. Can also be illustrated.

3.3 Hindered amine The hindered amine compound used in the present invention is an amine having one or more substituents on the carbon atom adjacent to the nitrogen atom. In particular, amines containing a piperidine group are preferred and are monomeric or oligomeric compounds. As the substituent, an alkyl group having 1 to 4 carbon atoms is preferable.

  Examples of the hindered amine having a piperidine skeleton include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-t-butyl-4- Hydroxybenzyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, dimethyl succinate.1- (2-hydroxyethyl) -4-hydroxy-2,2,6 , 6-tetramethylpiperidine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane condensate, N- (2,2,6,6- Tetramethyl-4-piperidyl) dodecyl succinimide, 3,9-bis [1,1-dimethyl-2-tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxyethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2-tris (1,2,2,6,6-pentamethyl- -Piperidyloxycarnyl) butylcarbonyloxyethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, poly [{6- (1,1,3,3-tetramethylbutyl) imino- 1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4- Piperidyl) imino}], N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino ] -6-chloro-1,3,5-triazine condensate, poly [6-morpholino-1,3,5-triazine-2,4-diyl] [4- (2,2,6,6-tetramethyl) Piperidyl) imino] hexamethi Ren- [4- (2,2,6,6-tetramethylpiperidyl) imino], poly [6-morpholino-1,3,5-triazine-2,4-diyl] [4- (1,2,2 , 6,6-pentamethylpiperidyl) imino] hexamethylene- [4- (1,2,2,6,6-pentamethylpiperidyl) imino] and the like, but is not limited thereto.

  Examples of hindered amine compounds containing a substituted piperidine group include Chimassorb 944, Chimassorb 119, Tinuvin 770, Tinuvin 791, Tinuvin 622, Tinuvin 144, and American Cyamide (commercially available from Ciba Specialty Chemicals). Cyasorb UV 3346, which is commercially available from

  These may be used alone or in combination of two or more. As a compounding quantity of this hindered amine light stabilizer, it is 0.01-0.20 weight part with respect to 100 weight part of polypropylene resin, Preferably it is 0.03-0.10 weight part. If it is less than 0.01 part by weight, it is not sufficient for ensuring the target transparency in the blending system of the present invention, and if it is 0.10 part by weight or more, there may be a problem in terms of appearance such as hue.

4). Dicarboxylic acid metal salt of bridged cyclic hydrocarbon compound As the dicarboxylic acid metal salt of bridged cyclic hydrocarbon compound, bicyclo [2,2,1] heptane, bicyclo [2,2,2] octane, bicyclo [3 , 2,1] octane, bicyclo [3,2,2] nonane, bridged cyclic hydrocarbon compounds such as bicyclo [4,2,2] decane, dicarboxylic acid alkali metal, alkaline earth metal metal salts Represent. Such a bridged cyclic hydrocarbon compound also includes an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, or a dicarboxylic acid salt composed of a multinuclear bridged cyclic hydrocarbon compound by connecting a plurality of positions.

  Specifically, bicyclo [2,2,1] heptane-2,3-dicarboxylate dilithium, bicyclo [2,2,1] heptane-2,3-dicarboxylate disodium, bicyclo [2,2,1 ] Dipotassium heptane-2,3-dicarboxylate, magnesium bicyclo [2,2,1] heptane-2,3-dicarboxylate, calcium bicyclo [2,2,1] heptane-2,3-dicarboxylate, bicyclo [ 2,2,2] octane-2,3-dicarboxylate disodium, bicyclo [2,2,2] octane-2,3-dicarboxylate dipotassium, bicyclo [2,2,2] octane-2,3- Dicarboxylic magnesium, disodium 5-methyl-bicyclo [2,2,2] octane-2,3-dicarboxylate, 5-methoxy-bicyclo [2,2,2] octane-2,3-dica Disodium bonate, disodium 5-phenoxy-bicyclo [2,2,2] octane-2,3-dicarboxylic acid, 5,6-dimethyl-bicyclo [2,2,2] octane-2,3-dicarboxylic acid Disodium, bicyclo [3,2,1] octane-2,3-dicarboxylic acid disodium, bicyclo [3,2,2] nonane-2,3-dicarboxylic acid disodium, bicyclo [3,2,2] nonane -6,7-dicarboxylic acid disodium, bicyclo [3,2,2] nonane-2,4-dicarboxylic acid disodium, 2,3,4-trimethyl-bicyclo [3,2,2] nonane-6,7 -Dicarboxylic acid salts of bridged cyclic hydrocarbon compounds such as disodium dicarboxylate.

  Among these, a carboxylate having a carboxylic acid group at an adjacent position is preferable, a bicyclo [2,2,2] octane-2,3-dicarboxylate is more preferable, and an alkali metal is more preferable. Salt.

  The amount of the dicarboxylic acid salt of the crosslinked cyclic hydrocarbon compound used is 0.01 to 0.10 parts by weight, preferably 0.02 to 0.05 parts by weight, with respect to 100 parts by weight of polypropylene. If it is less than 0.01, the effect of adding to the improvement of transparency and rigidity is not sufficient, and if it is 0.10 parts by weight or more, the effect of addition is saturated, which is not preferable in terms of economy, and on the contrary, the rigidity is increased. There is also a risk of damage.

5). Hydrotalcite Hydrotalcite does not contain hydrous basic carbonates such as magnesium, calcium, zinc, aluminum, bismuth or crystal water. Specifically, those of _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O structures. Examples of the synthetic _{product, Mg 0.7 Al 0.3 (CO 3} ) 0.16 · 0.54H 2 O, Mg 4.5 Al 2 (OH) 12 CO 3 · 3.5H 2 O, Mg 4.2 Al 2 (OH) 12.4 CO 3 Zn ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg ₁₄ Bi ₂ (OH) _29.6 · 4.2H ₂ O, and the like. A compound obtained by substituting a part of the raw material of the compound with zinc hydroxide can also be used. Specifically, magnesium, aluminum, hydroxide, carbonate, and hydrate are preferably used. These hydrotalcites are produced by dispersing oxides or carbonates of the respective composition elements and then firing them. The amount of CO ₃ or H ₂ O is usually controllable by firing at about 500 ° C.

6). Higher aliphatic carboxylic acid metal salt Examples of the higher aliphatic carboxylic acid include higher fatty acids having 10 to 22 carbon atoms or higher aliphatic oxyacids, such as lauric acid, palmitic acid, stearic acid, oleic acid and the like. As the chain monocarboxylic acid and aliphatic oxyacid, lactic acid, citric acid, hydroxystearic acid and the like having an alcoholic hydroxyl group in the side chain of the aliphatic carboxylic acid are preferable. As the metal, alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, calcium and barium, and metals such as zinc, aluminum, tin and lead can also be used.

  Preferred examples of these higher aliphatic carboxylic acid metal salts include magnesium stearate, calcium stearate, barium stearate, zinc stearate, aluminum stearate, calcium citrate, calcium lactate, calcium 12-hydroxystearate, calcium stearyl lactate, Examples include calcium lauryl lactate.

  The amount of the higher aliphatic carboxylic acid metal salt used is 0.01 to 0.20 parts by weight, preferably 0.02 to 0.08 parts by weight, based on 100 parts by weight of the polypropylene resin. If it is less than 0.01 part by weight, it is not sufficient to neutralize the influence of the polymerization catalyst residue and the like, and if it exceeds 0.20 part by weight, it is not preferable from the viewpoint of appearance such as inhibiting transparency.

  Further, either one of the hydrotalcites and the higher aliphatic carboxylic acid metal salt may be used, but both may be used in combination. The amount used in this case is 0.02 to 0.30 parts by weight in total with respect to 100 parts by weight of the polypropylene resin. The preferable amount in the case of using together is 0.04-0.13 weight part in total of both.

6). Additional ingredients (optional ingredients)
Other than the above components 1 to 5 are blended in the polypropylene resin composition used in the present invention, other additional components can be optionally added within a range that does not significantly impair the effects of the present invention.

  Such additional components include ethylene / propylene copolymer elastomer, ethylene / butene copolymer elastomer, ethylene / hexene copolymer elastomer, ethylene / α-olefin copolymer elastomer such as ethylene / octene copolymer elastomer, Ethylene / α-olefin / diene terpolymer elastomer such as propylene / ethylidene norbornene copolymer, styrene / butadiene block copolymer hydride (SEBS), styrene / isoprene block copolymer hydride (SEPS), etc. Elastomer components such as styrene elastomer, polyethylene components such as HDPE, LLDPE, LDPE, polyethylene wax, phenolic and phosphorus antioxidants, benzophenone, benzoate, benzotriazole Type weather resistance inhibitors, lubricants such as oleic acid amide and stearic acid amide, higher fatty acid esters of polyhydric alcohols and their derivatives, higher aliphatic amine derivatives, ethylene oxide adducts of higher fatty acid amides and their derivatives, alkylbenzene sulfonic acids Antistatic agents such as salts and derivatives thereof, colored substances such as quinacridone, perylene, phthalocyanine, titanium oxide, and carbon black, various foams such as inorganic fillers such as talc, inorganic filler, and glass fiber, chemical foaming agents, and physical foaming agents An agent can be mentioned.

7). Blending method Polypropylene resin composition constituting the polypropylene resin molded body of the present invention is set by using an extruder, Banbury mixer, roll, Brabender plastograph, kneader, etc. Although it manufactures by knead | mixing at the temperature of 180-250 degreeC, it is preferable to manufacture especially using a twin-screw extruder among these.

  Specifically, 100 parts by weight of polymer powder (polypropylene resin), 0.01 to 0.50 parts by weight of various nucleating agents, 0.01 to 0.2 parts by weight of amine compounds such as dialkylhydroxylamine, and crosslinked cyclic 0 to 0.10 parts by weight of dicarboxylic acid metal salt of hydrocarbon compound, 0 to 0.30 part by weight of hydrotalcite, 0 to 0.20 part by weight of higher aliphatic carboxylic acid metal salt, other optional components, etc. It is preferable to add them in an amount, sequentially or all at once and mix in a solid state using a Henschel mixer. Then, it is preferable to heat and melt and granulate with a twin screw extruder or the like.

8). Molding Method The polypropylene resin composition produced by the above method can be processed into a product having a desired shape by a known general molding method. For example, methods such as injection molding, compression injection molding, extrusion molding, and blow molding can be applied. Examples of uses of molded products include packaging containers such as foods, cosmetics, and pharmaceuticals, caps, packaging films, sheets, laminates, and the like that require high transparency and sufficient rigidity.

  Examples of the product shape include cylindrical, box-shaped containers, cylindrical bodies, caps, non-stretched, uniaxially stretched or biaxially stretched films, bags or sheets.

9. Polymer physical properties and evaluation method of molded product (1) Isotactic pentad fraction [mmmm]: The ¹³ C-NMR method described in the text was followed.
(2) Melt flow rate (MFR): Measured according to JIS-K6921-2: 1997 appendix (230 ° C., 21.18 N load).
(3) Ethylene content: Followed by ¹³ C-NMR method. It calculated using the spectrum which measured said [mmmm].
(4) Molecular weight distribution: According to the GPC method described in the text.
(5) Melting point: Using DSC manufactured by Seiko Co., Ltd., taking 5.0 mg of sample, holding it at 200 ° C. for 5 minutes, crystallizing it to 40 ° C. at a cooling rate of 10 ° C./minute, and holding for 1 minute Further, evaluation was made based on the peak temperature when melted at a heating rate of 10 ° C./min.
(6) Haze: Measured at 23 ° C. using a test piece having a thickness of 2 mm in accordance with JIS K7105. In the case of haze of a film molded body, a cast film having a thickness of 60 μm was manufactured and measured using a T-die molding machine.
(7) Flexural modulus: measured at 23 ° C. according to JIS K7203.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated still in detail, this invention is not limited to a following example, unless the summary is exceeded.

(1) Polypropylene resin [Production Example 1] Production of propylene random copolymer (PP-1) a. Metallocene compound A racemic dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride is synthesized based on the description in Example 1 of JP-A No. 2002-20430. did.

B. Chemical treatment of clay mineral In a solution obtained by mixing 218.1 g of sulfuric acid (96%) and 130.4 g of magnesium sulfate with 909 ml of demineralized water, 200.03 g of commercially available montmorillonite (Kunimine Industries, Kunipia F) was dispersed at 100 ° C. Stir for 2 hours. This water slurry of montmorillonite was adjusted to a solid content concentration of 12%, and spray granulation was performed with a spray dryer to obtain particles. Thereafter, the particles were dried under reduced pressure at 200 ° C. for 2 hours.

C. Preparation of solid catalyst component After the inside of a 1 liter stirred autoclave was sufficiently substituted with propylene, 230 ml of dehydrated and deoxygenated heptane was introduced, and the system temperature was maintained at 40 ° C. 10 g of the above chemically treated clay slurried with toluene was added thereto. Further, in another container, 0.15 mmol of the above metallocene compound and 1.5 mmol of triisobutylaluminum mixed under toluene were added. Here, propylene was introduced at a rate of 10 g / hour for 120 minutes, and then polymerization was continued for 120 minutes. Further, the solvent was removed and dried under nitrogen to obtain a solid catalyst component. This solid catalyst component contained 1.9 g of polypropylene per 1 g of the solid component.

D. Propylene / Ethylene Copolymerization After the inside of a stirring autoclave having an internal volume of 200 l was sufficiently substituted with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, 1.35 kg of ethylene, and 6 L of hydrogen (as a standard state volume) were added, and the internal temperature was maintained at 30 ° C. Next, 2.4 g of the solid catalyst component was injected with argon to initiate polymerization, and the temperature was raised to 70 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Here, 100 ml of ethanol was added to stop the reaction. The residual gas was purged to obtain 18 kg of a propylene / ethylene random copolymer (PP-1).

  The MFR of the polymer was 9 g / 10 min, the melting point was 132 ° C., [mmmm] = 0.981, and the ethylene content was 2.3% by weight.

[Production Example 2] Production of Propylene Random Copolymer (PP-2) In Production Example 1, the amount of hydrogen 6L was changed to 12L, and the others were carried out in accordance with Production Example 1 using a propylene / ethylene copolymer. It was.

  The obtained polymer had an MFR of 30 g / 10 min, a melting point of 131 ° C., [mmmm] = 0.981, and an ethylene content of 2.3% by weight.

[Production Example 3] Production of propylene random copolymer (PP-3) a. Production of solid catalyst component 100 ml of dehydrated and deoxygenated toluene was introduced into a sufficiently nitrogen-substituted flask, and then 10 g of Mg (OEt) ₂ was introduced into a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of 2,2-diisopropyl-1,3-dimethoxypropane was introduced, and the temperature was further raised to 110 ° C. and reacted for 3 hours. After completion of the reaction, it was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 20 ml of TiCl ₄ and 100 ml of toluene were further introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid component was obtained by thoroughly washing with n-heptane. The titanium content of this product was 2.7% by weight.

Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 5 g of the solid component synthesized above was introduced, and (C ₆ H ₁₁ ) CH ₃ Si (OCH ₃ ) ₂ 2 was introduced. 0.7 ml and 1.7 g Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. The titanium content of this product was 2.3% by weight.

B. Copolymerization of propylene / ethylene A stainless steel autoclave with an internal volume of 10 L having a stirring and temperature control device is heated and dried under vacuum, cooled to room temperature and substituted with propylene, and then Al (C2H5) 3 is added as component (B). 1.65 g, 5000 ml of hydrogen were introduced, then 3 kg of liquid propylene were introduced, ethylene was added by 1 bar of differential pressure, the internal temperature was adjusted to 70 ° C., and 20 mg of the component (A) produced above was injected. Polymerized. After 2 hours, 30 ml of ethanol was injected to terminate the polymerization, and the resulting polymer was recovered and dried. As a result, 1.25 kg of polymer was obtained.

  The obtained polymer had an MFR of 10 g / 10 min, a polymer bulk density of 0.45 g / cc, a melting point of 147 ° C., [mmmm] = 0.975, and an ethylene content of 2.3% by weight.

[Production Example 4] Production of propylene homopolymer (PP-4) In Production Example 1, the amount of hydrogen was increased from 6 L to 12 L, ethylene was not supplied, and the others were homopolymerized in accordance with Production Example 1 Went.

  The obtained polymer had an MFR of 30 g / 10 min, a melting point of 154 ° C., and [mmmm] = 0.985.

[Production Example 5] Production of propylene-based random copolymer (PP-5) In Production Example 1, the amount of ethylene supplied was increased from 1.35 kg to 1.90 kg, and the others were propylene / ethylene according to Production Example 1. Was copolymerized.

  The obtained polymer had an MFR of 7 g / 10 min, an ethylene content of 3.4% by weight, a melting point of 124 ° C., and [mmmm] = 0.978.

[Production Example 6] Production of Propylene Random Copolymer (PP-6) In Production Example 1, 1.35 kg of ethylene was reduced to 1.22 kg, and the others were propylene / ethylene according to Production Example 1. Was copolymerized.

  The obtained polymer had an MFR of 7 g / 10 min, an ethylene content of 2.1 wt%, a melting point of 135 ° C., and [mmmm] = 0.981.

  Table 1 shows the physical properties of the polypropylene resins (PP-1 to 6) and commercially available polypropylene (PP-7: Polypropylene FG3DA equivalent powder manufactured by Nippon Polychem Co., Ltd.) produced in the above Production Examples 1 to 6. .

(2) Various compounding agents The various compounding agents compounded with the propylene resin are summarized in Table 2.

[Examples 1 to 16]
In PP-1, 2, 3, 4 (polymer powder), various compounding agents are collectively added at the blending ratios shown in Table 3-1 and Table 3-2, and in a solid state using a Henschel mixer. Was mixed. Thereafter, the mixture was melt-mixed at 200 ° C. using a twin screw extruder (TEM-35, manufactured by Toshiba Machine Co., Ltd.) to obtain a pellet of a polypropylene resin composition. Dioctylhydroxylamine was added in the form of an equal weight mixture (FS301) with a phosphorus processing stabilizer.

  Using the pellets obtained above as a raw material, an injection molding machine (manufactured by Toshiba Machine Co., EC-100) was used for injection molding under the condition of a resin temperature of 220 ° C. and a flat test piece of 120 mm × 80 mm × 2 mm and JIS K7203. A test piece having a thickness of 4 mm for measuring the flexural modulus in accordance with the above was prepared. Using this, haze and bending elastic modulus were measured. The evaluation results of the injection molded products are shown in Tables 3-1 and 3-2.

  From Examples 1 to 7, a molded product having a haze of less than 35% and a flexural modulus of 900 to 1200 MPa can be easily obtained by using the propylene / ethylene copolymer as a polypropylene-based resin. You can see that On the other hand, from Examples 8 to 16, a molded product having a haze of less than 35 to 50% and a flexural modulus of 1500 to 2500 MPa can be easily obtained by using the propylene homopolymer as the polypropylene resin. It can be seen that

[Comparative Examples 1-6]
In the same manner as in Example 1 except that various compounding agents are added to PP-1, 2, 4 (polymer powder) at a blending ratio shown in Table 4 without adding dialkylhydroxylamine or hindered amine. Carried out. The evaluation results are shown in Table 4.

[Examples 17 to 24]
In PP-5 and PP-6, 100 parts by weight, various compounding agents shown in Table 5 were blended at a predetermined ratio, mixed at 750 rpm for 2 minutes with a Henschel mixer, and then extruded at a temperature of 200 mm using a 30 mmφ single screw extruder. Pelletized at 0 ° C. The obtained pellets were put into a 35 mmφ single-layer T-die molding machine manufactured by Plako, melt-extruded from a T-die having a width of 300 mm at an extrusion temperature of 220 ° C., and cooled and solidified while being wound around a chill roll having a diameter of 300 mm adjusted to 50 ° C. A cast film having a thickness of 60 μm was produced at a speed of 8 m / min. Subsequently, the air knife surface of the film was subjected to corona treatment so that the wetting tension according to JIS K6768 immediately after molding was 42 mN / m, and the physical properties of the film were measured with the corona-treated surface as the front surface and the opposite surface as the back surface. Table 5 shows the evaluation results of the film.

[Comparative Examples 7 to 11]
With respect to PP-5 or PP-7, a film was produced in the same manner as in Example 17 with the formulation shown in Table 6. Table 6 shows the evaluation results of the film.

  Comparative Example 7 has poor transparency because neither a nucleating agent nor an amine is added. In Comparative Example 8, a sorbitol nucleating agent is added, but the transparency is poor because no amine is added. In Comparative Example 9, the amine is added but the sorbitol nucleating agent is not added, so the transparency is poor.

The propylene-based resin composition of the present invention has an excellent balance between rigidity and transparency as an injection-molded product or film, and can be used in fields such as food containers and medical containers.

Claims (12)

  A sorbitol nucleating agent and a phosphate nucleating agent with respect to 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. 0.01 to 0.50 parts by weight of at least one nucleating agent selected from: 0.01 to 0.20 parts by weight of at least one amine compound selected from dialkylhydroxylamine, hydroxyalkyl group-containing amine and hindered amine A polypropylene resin composition to be contained.   The sorbitol nucleating agent is 0.01 to 0.50 with respect to 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. A polypropylene resin composition containing parts by weight and 0.01 to 0.20 parts by weight of a dialkylhydroxylamine or hydroxyalkyl group-containing amine.   The sorbitol nucleating agent is 0.01 to 0.50 with respect to 100 parts by weight of a polypropylene resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. A polypropylene resin composition containing parts by weight and 0.01 to 0.20 parts by weight of a hindered amine.   Phosphate-based nucleating agent 0.01 to 0 with respect to 100 parts by weight of polypropylene-based resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. A polypropylene resin composition containing 30 parts by weight and 0.01 to 0.10 parts by weight of a dialkylhydroxylamine or hydroxyalkyl group-containing amine.   Phosphate-based nucleating agent 0.01 to 0 with respect to 100 parts by weight of polypropylene-based resin having an isotactic pentad fraction of 0.960 or more and a molecular weight distribution (Mw / Mn) of 4.5 or less. Polypropylene resin composition containing 30 parts by weight and hindered amine 0.01 to 0.10 parts by weight.   The polypropylene resin composition according to any one of claims 1 to 5, further comprising 0.01 to 0.10 parts by weight of a dicarboxylic acid metal salt of a crosslinked cyclic hydrocarbon compound. .   The polypropylene resin composition, wherein the polypropylene resin composition according to any one of claims 1 to 6 further contains 0.01 to 0.30 parts by weight of hydrotalcites.   The polypropylene resin composition in which the polypropylene resin composition according to any one of claims 1 to 7 further contains 0.01 to 0.20 parts by weight of a higher aliphatic carboxylic acid metal salt.   The polypropylene resin composition according to claim 8, wherein the total amount of the hydrotalcite and the higher aliphatic carboxylic acid metal salt is 0.02 to 0.30 parts by weight.   The polypropylene resin composition according to any one of claims 1 to 9, wherein the polypropylene resin is obtained using a metallocene catalyst.   The food container or medical container formed by shape | molding the polypropylene resin composition of any one of Claims 1-10.   A substantially unstretched film, a uniaxially stretched film, a biaxially stretched film, an injection molded body, an extruded molded body, and a blown body formed by molding the polypropylene resin composition according to any one of claims 1 to 10. Molded body or sheet.